Supplementary Material (ESI) for Dalton Transactions This journal is (c) The Royal Society of Chemistry 2002 data_s92 _database_code_CSD 181362 _journal_coden_Cambridge 186 _publ_requested_journal 'Dalton Transactions' loop_ _publ_author_name 'Skabara, Peter' 'Allen, David W.' 'Berridge, Rory' 'Bricklebank, Neil' 'Cerrada, Elena' 'Hursthouse, Michael B.' 'Laguna, Mariano' 'Light, Mark E.' 'Moreno, Ana' _publ_contact_author_name 'Dr Peter Skabara' _publ_contact_author_address ; Chemistry University of Manchester Oxford Road Manchester M13 9PL UNITED KINGDOM ; _publ_contact_author_email 'PETER.SKABARA@MAN.AC.UK' _publ_section_title ; A new family of sulfur-rich ligands based on the dmit system: synthesis and metal complexation of 4-4'-covalently bridged bis(2-thioxo-1,3-dithiol-5-thiolato) units ; _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_formula_moiety ? _chemical_formula_sum 'C24 H18 N2 Ni S10' _chemical_formula_weight 713.71 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source 'C' 'C' 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'H' 'H' 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'S' 'S' 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'Ni' 'Ni' 0.3393 1.1124 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'N' 'N' 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Triclinic _symmetry_space_group_name_H-M P-1 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 9.5662(6) _cell_length_b 12.5254(8) _cell_length_c 14.0131(8) _cell_angle_alpha 76.558(3) _cell_angle_beta 86.314(3) _cell_angle_gamma 67.969(3) _cell_volume 1513.32(16) _cell_formula_units_Z 2 _cell_measurement_temperature 150(2) _cell_measurement_reflns_used 4319 _cell_measurement_theta_min 2.95 _cell_measurement_theta_max 23.25 _exptl_crystal_description ? _exptl_crystal_colour ? _exptl_crystal_size_max 0.20 _exptl_crystal_size_mid 0.20 _exptl_crystal_size_min 0.10 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.566 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 728 _exptl_absorpt_coefficient_mu 1.350 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.7740 _exptl_absorpt_correction_T_max 0.8768 _exptl_special_details ; SORTAV (Blessing, 1997) ; _diffrn_ambient_temperature 150(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'Bruker Nonius FR591 Rotating anode' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Bruker Nonius Kappa CCD' _diffrn_measurement_method 'phi and omega scans to fill Ewald sphere' _diffrn_detector_area_resol_mean '9.091 pixels/mm' _diffrn_standards_number 0 _diffrn_standards_interval_count 0 _diffrn_standards_interval_time 0 _diffrn_standards_decay_% 0 _diffrn_reflns_number 18864 _diffrn_reflns_av_R_equivalents 0.1189 _diffrn_reflns_av_sigmaI/netI 0.0918 _diffrn_reflns_limit_h_min -10 _diffrn_reflns_limit_h_max 10 _diffrn_reflns_limit_k_min -13 _diffrn_reflns_limit_k_max 13 _diffrn_reflns_limit_l_min -15 _diffrn_reflns_limit_l_max 15 _diffrn_reflns_theta_min 2.95 _diffrn_reflns_theta_max 23.25 _reflns_number_total 4319 _reflns_number_gt 2692 _reflns_threshold_expression >2sigma(I) _computing_data_collection ; DENZO (Otwinowski and Minor, 1997), COLLECT (Hooft, 1998) ; _computing_cell_refinement ; DENZO (Otwinowski and MInor, 1997), COLLECT (Hooft, 1998) ; _computing_data_reduction ; DENZO (Otwinowski and MInor, 1997), COLLECT (Hooft, 1998), MAXUS (Mackay et al., 1998) ; _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'ORTEP-III (Burnett et al., 1996)' _computing_publication_material 'WINGX (Farrugia (1998)' _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme 'calc w=1/[\s^2^(Fo^2^)+(0.0599P)^2^+0.1975P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 4319 _refine_ls_number_parameters 334 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.1009 _refine_ls_R_factor_gt 0.0517 _refine_ls_wR_factor_ref 0.1364 _refine_ls_wR_factor_gt 0.1149 _refine_ls_goodness_of_fit_ref 1.017 _refine_ls_restrained_S_all 1.017 _refine_ls_shift/su_max 0.000 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Ni1 Ni 0.65980(8) 0.18777(7) 0.21538(5) 0.0422(3) Uani 1 d . . . S1 S 0.62186(17) 0.20817(16) 0.04267(11) 0.0560(5) Uani 1 d . . . S2 S 0.39614(16) 0.34932(14) 0.20167(11) 0.0429(4) Uani 1 d . . . S10 S 0.69610(18) 0.17915(16) 0.38416(11) 0.0534(5) Uani 1 d . . . S6 S 0.81507(17) 0.32200(15) 0.18179(11) 0.0473(4) Uani 1 d . . . S5 S 0.13967(17) 0.36425(16) 0.07604(12) 0.0534(5) Uani 1 d . . . S3 S 0.3383(2) 0.22544(16) -0.04830(12) 0.0585(5) Uani 1 d . . . S9 S 0.9494(2) 0.18917(18) 0.48614(12) 0.0661(6) Uani 1 d . . . S7 S 1.05010(19) 0.32013(18) 0.31839(13) 0.0658(6) Uani 1 d . . . S4 S 0.0090(2) 0.3099(2) -0.08580(15) 0.0850(7) Uani 1 d . . . S8 S 1.2023(2) 0.2638(2) 0.51319(16) 0.0973(8) Uani 1 d . . . C3 C 0.3319(6) 0.3191(6) 0.1007(4) 0.0452(16) Uani 1 d . . . N1 N 0.8694(5) 0.0550(4) 0.2042(3) 0.0464(13) Uani 1 d . . . C2 C 0.1526(7) 0.2999(6) -0.0211(4) 0.0518(17) Uani 1 d . . . C1 C 0.4283(6) 0.2583(5) 0.0401(4) 0.0431(15) Uani 1 d . . . C14 C 0.8457(6) 0.2242(5) 0.3770(4) 0.0456(16) Uani 1 d . . . C12 C 0.8956(6) 0.2834(6) 0.2990(4) 0.0474(16) Uani 1 d . . . C13 C 1.0724(7) 0.2609(7) 0.4420(5) 0.0610(19) Uani 1 d . . . C4 C 0.4083(7) 0.4948(5) 0.1501(5) 0.0571(18) Uani 1 d . . . H4A H 0.4801 0.4898 0.0957 0.068 Uiso 1 calc R . . H4B H 0.3082 0.5536 0.1245 0.068 Uiso 1 calc R . . C10 C 0.6111(7) 0.5249(5) 0.2373(4) 0.0489(16) Uani 1 d . . . C5 C 0.4622(7) 0.5301(5) 0.2325(5) 0.0475(16) Uani 1 d . . . C15 C 0.9623(7) 0.0660(6) 0.1301(5) 0.0535(17) Uani 1 d . . . H15 H 0.9350 0.1398 0.0839 0.064 Uiso 1 calc R . . C11 C 0.7240(7) 0.4832(6) 0.1630(5) 0.0570(18) Uani 1 d . . . H11A H 0.8031 0.5163 0.1631 0.068 Uiso 1 calc R . . H11B H 0.6736 0.5151 0.0973 0.068 Uiso 1 calc R . . C19 C 0.9117(7) -0.0498(6) 0.2682(4) 0.0550(18) Uani 1 d . . . H19 H 0.8503 -0.0600 0.3230 0.066 Uiso 1 calc R . . N2 N 0.5409(5) 0.0738(4) 0.2617(3) 0.0442(12) Uani 1 d . . . C16 C 1.0937(7) -0.0222(7) 0.1169(5) 0.063(2) Uani 1 d . . . H16 H 1.1552 -0.0098 0.0628 0.076 Uiso 1 calc R . . C24 C 0.4527(6) 0.0837(6) 0.3397(4) 0.0473(16) Uani 1 d . . . H24 H 0.4390 0.1472 0.3700 0.057 Uiso 1 calc R . . C9 C 0.6519(9) 0.5599(6) 0.3154(5) 0.066(2) Uani 1 d . . . H9 H 0.7514 0.5581 0.3197 0.079 Uiso 1 calc R . . C6 C 0.3646(8) 0.5672(6) 0.3038(5) 0.063(2) Uani 1 d . . . H6 H 0.2641 0.5709 0.2998 0.076 Uiso 1 calc R . . C20 C 0.5560(8) -0.0158(7) 0.2201(5) 0.067(2) Uani 1 d . . . H20 H 0.6166 -0.0245 0.1639 0.081 Uiso 1 calc R . . C8 C 0.5503(11) 0.5969(7) 0.3862(6) 0.080(2) Uani 1 d . . . H8 H 0.5801 0.6209 0.4385 0.096 Uiso 1 calc R . . C18 C 1.0410(8) -0.1434(6) 0.2575(5) 0.065(2) Uani 1 d . . . H18 H 1.0646 -0.2180 0.3020 0.077 Uiso 1 calc R . . C17 C 1.1353(8) -0.1280(7) 0.1821(5) 0.072(2) Uani 1 d . . . H17 H 1.2278 -0.1902 0.1757 0.086 Uiso 1 calc R . . C7 C 0.4074(9) 0.5994(6) 0.3816(6) 0.073(2) Uani 1 d . . . H7 H 0.3379 0.6230 0.4313 0.088 Uiso 1 calc R . . C23 C 0.3806(7) 0.0072(6) 0.3786(5) 0.0583(18) Uani 1 d . . . H23 H 0.3201 0.0168 0.4348 0.070 Uiso 1 calc R . . C22 C 0.3986(9) -0.0826(7) 0.3341(6) 0.079(2) Uani 1 d . . . H22 H 0.3487 -0.1360 0.3583 0.094 Uiso 1 calc R . . C21 C 0.4877(10) -0.0959(7) 0.2552(6) 0.093(3) Uani 1 d . . . H21 H 0.5029 -0.1594 0.2246 0.111 Uiso 1 calc R . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Ni1 0.0368(4) 0.0483(6) 0.0387(4) -0.0058(4) 0.0040(3) -0.0156(4) S1 0.0387(9) 0.0752(14) 0.0434(9) -0.0123(9) 0.0051(7) -0.0104(9) S2 0.0371(8) 0.0514(11) 0.0421(9) -0.0127(7) 0.0011(7) -0.0173(8) S10 0.0517(10) 0.0754(13) 0.0397(9) -0.0079(8) 0.0055(8) -0.0345(9) S6 0.0402(9) 0.0595(12) 0.0440(9) -0.0060(8) -0.0004(7) -0.0235(8) S5 0.0393(9) 0.0761(13) 0.0513(10) -0.0188(9) 0.0015(8) -0.0261(9) S3 0.0675(11) 0.0614(12) 0.0505(10) -0.0181(9) -0.0047(9) -0.0241(10) S9 0.0606(11) 0.0972(16) 0.0433(10) -0.0103(10) -0.0065(9) -0.0343(11) S7 0.0486(10) 0.0973(16) 0.0613(11) -0.0124(10) -0.0038(9) -0.0405(11) S4 0.0814(14) 0.1146(19) 0.0777(14) -0.0174(13) -0.0232(12) -0.0557(14) S8 0.0784(14) 0.157(2) 0.0777(14) -0.0327(15) -0.0154(12) -0.0606(16) C3 0.033(3) 0.063(5) 0.045(4) -0.020(3) -0.003(3) -0.020(3) N1 0.038(3) 0.051(4) 0.039(3) -0.004(3) 0.006(2) -0.009(3) C2 0.049(4) 0.061(5) 0.054(4) -0.011(3) -0.004(3) -0.030(3) C1 0.043(3) 0.050(4) 0.035(3) -0.006(3) -0.005(3) -0.017(3) C14 0.040(3) 0.054(4) 0.041(4) -0.012(3) -0.003(3) -0.015(3) C12 0.035(3) 0.061(5) 0.044(4) -0.007(3) 0.001(3) -0.019(3) C13 0.047(4) 0.092(6) 0.051(4) -0.025(4) -0.001(3) -0.027(4) C4 0.055(4) 0.053(5) 0.066(4) 0.001(3) -0.016(3) -0.028(4) C10 0.051(4) 0.038(4) 0.054(4) 0.001(3) -0.003(3) -0.020(3) C5 0.053(4) 0.030(4) 0.056(4) -0.009(3) -0.004(3) -0.010(3) C15 0.040(4) 0.061(5) 0.052(4) -0.012(3) 0.005(3) -0.013(4) C11 0.060(4) 0.052(5) 0.060(4) 0.009(3) -0.018(4) -0.031(4) C19 0.055(4) 0.050(5) 0.047(4) -0.009(4) 0.006(3) -0.008(4) N2 0.041(3) 0.046(3) 0.043(3) -0.007(3) 0.005(3) -0.016(3) C16 0.049(4) 0.088(6) 0.051(4) -0.026(4) 0.008(3) -0.018(4) C24 0.043(4) 0.054(5) 0.048(4) -0.013(3) 0.006(3) -0.021(3) C9 0.075(5) 0.063(5) 0.071(5) -0.011(4) -0.017(4) -0.038(4) C6 0.056(4) 0.048(5) 0.086(5) -0.022(4) -0.007(4) -0.013(4) C20 0.074(5) 0.070(5) 0.075(5) -0.035(4) 0.023(4) -0.037(4) C8 0.104(7) 0.069(6) 0.073(6) -0.019(4) -0.008(5) -0.035(5) C18 0.075(5) 0.053(5) 0.053(4) -0.005(4) -0.009(4) -0.012(4) C17 0.053(4) 0.081(6) 0.059(5) -0.021(5) -0.005(4) 0.003(4) C7 0.078(6) 0.061(5) 0.080(5) -0.033(4) 0.020(5) -0.018(4) C23 0.061(4) 0.058(5) 0.053(4) -0.009(4) 0.013(4) -0.023(4) C22 0.092(6) 0.073(6) 0.090(6) -0.026(5) 0.030(5) -0.051(5) C21 0.131(8) 0.077(6) 0.107(7) -0.056(5) 0.047(6) -0.067(6) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Ni1 N1 2.095(5) . ? Ni1 N2 2.109(5) . ? Ni1 S10 2.3842(17) . ? Ni1 S1 2.4105(17) . ? Ni1 S2 2.5585(17) . ? Ni1 S6 2.5827(18) . ? S1 C1 1.717(6) . ? S2 C3 1.749(5) . ? S2 C4 1.841(6) . ? S10 C14 1.714(6) . ? S6 C12 1.743(6) . ? S6 C11 1.835(7) . ? S5 C2 1.712(6) . ? S5 C3 1.741(5) . ? S3 C2 1.734(6) . ? S3 C1 1.757(5) . ? S9 C13 1.737(7) . ? S9 C14 1.752(5) . ? S7 C13 1.711(7) . ? S7 C12 1.757(6) . ? S4 C2 1.644(6) . ? S8 C13 1.659(6) . ? C3 C1 1.351(8) . ? N1 C19 1.338(7) . ? N1 C15 1.340(7) . ? C14 C12 1.340(8) . ? C4 C5 1.509(8) . ? C10 C9 1.395(8) . ? C10 C5 1.407(8) . ? C10 C11 1.487(9) . ? C5 C6 1.362(9) . ? C15 C16 1.363(8) . ? C19 C18 1.377(8) . ? N2 C20 1.337(8) . ? N2 C24 1.337(7) . ? C16 C17 1.355(10) . ? C24 C23 1.377(8) . ? C9 C8 1.377(10) . ? C6 C7 1.381(9) . ? C20 C21 1.377(10) . ? C8 C7 1.361(10) . ? C18 C17 1.371(9) . ? C23 C22 1.360(9) . ? C22 C21 1.354(10) . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag N1 Ni1 N2 96.17(19) . . ? N1 Ni1 S10 94.61(13) . . ? N2 Ni1 S10 87.79(13) . . ? N1 Ni1 S1 87.01(13) . . ? N2 Ni1 S1 94.88(13) . . ? S10 Ni1 S1 176.71(7) . . ? N1 Ni1 S2 171.09(13) . . ? N2 Ni1 S2 83.39(14) . . ? S10 Ni1 S2 94.26(6) . . ? S1 Ni1 S2 84.16(5) . . ? N1 Ni1 S6 83.23(15) . . ? N2 Ni1 S6 172.75(13) . . ? S10 Ni1 S6 85.05(6) . . ? S1 Ni1 S6 92.31(6) . . ? S2 Ni1 S6 98.32(6) . . ? C1 S1 Ni1 98.20(19) . . ? C3 S2 C4 102.4(3) . . ? C3 S2 Ni1 96.9(2) . . ? C4 S2 Ni1 109.7(2) . . ? C14 S10 Ni1 100.5(2) . . ? C12 S6 C11 101.6(3) . . ? C12 S6 Ni1 97.7(2) . . ? C11 S6 Ni1 121.5(2) . . ? C2 S5 C3 98.0(3) . . ? C2 S3 C1 98.7(3) . . ? C13 S9 C14 98.1(3) . . ? C13 S7 C12 97.2(3) . . ? C1 C3 S5 117.4(4) . . ? C1 C3 S2 121.7(4) . . ? S5 C3 S2 120.8(4) . . ? C19 N1 C15 116.5(5) . . ? C19 N1 Ni1 120.6(4) . . ? C15 N1 Ni1 122.7(4) . . ? S4 C2 S5 125.3(4) . . ? S4 C2 S3 122.5(4) . . ? S5 C2 S3 112.1(3) . . ? C3 C1 S1 128.0(4) . . ? C3 C1 S3 113.6(4) . . ? S1 C1 S3 118.4(3) . . ? C12 C14 S10 129.0(4) . . ? C12 C14 S9 114.5(4) . . ? S10 C14 S9 116.5(4) . . ? C14 C12 S6 122.5(4) . . ? C14 C12 S7 117.2(4) . . ? S6 C12 S7 120.2(4) . . ? S8 C13 S7 124.7(4) . . ? S8 C13 S9 122.4(4) . . ? S7 C13 S9 112.8(3) . . ? C5 C4 S2 106.8(4) . . ? C9 C10 C5 117.9(6) . . ? C9 C10 C11 119.9(6) . . ? C5 C10 C11 122.2(6) . . ? C6 C5 C10 119.4(6) . . ? C6 C5 C4 119.2(6) . . ? C10 C5 C4 121.4(6) . . ? N1 C15 C16 123.9(6) . . ? C10 C11 S6 114.9(4) . . ? N1 C19 C18 122.4(6) . . ? C20 N2 C24 116.4(6) . . ? C20 N2 Ni1 122.9(5) . . ? C24 N2 Ni1 120.5(4) . . ? C17 C16 C15 119.1(7) . . ? N2 C24 C23 123.8(6) . . ? C8 C9 C10 121.2(7) . . ? C5 C6 C7 122.0(7) . . ? N2 C20 C21 123.0(7) . . ? C7 C8 C9 120.3(7) . . ? C17 C18 C19 119.5(7) . . ? C16 C17 C18 118.6(7) . . ? C8 C7 C6 119.1(8) . . ? C22 C23 C24 117.9(6) . . ? C21 C22 C23 120.0(7) . . ? C22 C21 C20 118.9(7) . . ? _diffrn_measured_fraction_theta_max 0.993 _diffrn_reflns_theta_full 23.25 _diffrn_measured_fraction_theta_full 0.993 _refine_diff_density_max 0.502 _refine_diff_density_min -0.463 _refine_diff_density_rms 0.085